Pyridine base synthesis

- Reilly Industries, Inc.

A base synthesis process and catalyst for the preparation of pyridine or its alkylpyridine derivatives involving the catalytic reaction of one or more aldehydes and/or ketones containing from one to about five carbon atoms, with at least one reactant having more than one carbon atom, with ammonia in the gas phase. The catalyst comprises an effective amount of a large-pore zeolite having been prepared with a silica to alumina ratio of at least 15, and at least a first dimension having first channels formed by twelve-membered rings, and a second dimension having second channels formed by ten- or twelve-membered rings which intersect the first channels. The preferred zeolite is a zeolite having the structure of zeolite beta.

Skip to:  ·  Claims  ·  References Cited  · Patent History  ·  Patent History

Claims

1. A base synthesis process for the preparation of pyridine or its alkylpyridine derivatives comprising reacting one or more aldehydes and/or ketones or mixtures thereof containing from 1 to about 5 carbon atoms, with at least one reactant having more than 1 carbon atom, with ammonia in the gas phase and in the presence of an effective amount of a zeolite catalyst having a first dimension having channels formed by twelve-membered rings, and a second dimension having channels formed by ten- or twelve-membered rings, said zeolite catalyst having been prepared with a silica to alumina ratio of at least 15.

2. The process of claim 1 in which the organic reactants comprise one or more members selected from the group consisting of acetaldehyde, propionaldehyde, acetone, methylethylketone, butyraldehyde, and crotonaldehyde.

3. The process of claim 2 in which the organic reactants comprise acetaldehyde and formaldehyde, and comprising the additional step of recovering pyridine and beta-picoline as the products of said reacting.

4. The process of claim 3 in which the reactants also include methanol.

5. The process of claim 2 in which the zeolite as a constraint index less than 1 and a spaciousness index in the range of 10 to 20.

6. The process of claim 1 in which the reactant is acetaldehyde, and additionally comprising recovering alpha- and gamma-picoline as the products of said reacting.

7. The process of claim 1 in which the zeolite has the structure of zeolite beta.

8. The process of claim 1 in which the zeolite has been treated with a metal ion or compound.

9. The process of claim 1 in which the zeolite is in acidic form.

10. The process of claim 1, wherein the zeolite is formulated with a binder containing silica, alumina, or a combination thereof.

11. The process of claim 1 in which the reactants are a mixture of acetaldehyde, formaldehyde and propionaldehyde, and additionally comprising recovering pyridine and beta-picoline as the products of said reacting.

12. A catalyst for use in base synthesis processes for the preparation of pyridine or its alkylpyridine derivatives, comprising an effective amount of a zeolite catalyst having a silica to alumina molar ratio of at least 15, a first dimension having pores formed by twelve-membered rings, and a second dimension having pores formed by ten- or twelve-membered rings, said zeolite having been treated with one or more ions of or compounds containing lead, cobalt, tin, cadmium, gallium, thallium or platinum.

13. The catalyst of claim 12, which includes the zeolite and a binder containing silica, alumina, or a combination thereof.

14. The catalyst of claim 12, wherein the zeolite has the structure of zeolite beta.

15. The catalyst of claim 13, wherein the zeolite is zeolite beta.

16. A base synthesis process for preparing pyridine, or its alkylpyridine derivatives, comprising reacting one or more aldehydes, and/or ketones or mixtures thereof, containing from 1 to about 5 carbon atoms, with at least one reactant having more than 1 carbon atom, with ammonia in the gas phase and in the presence of an effective amount of a zeolite catalyst having the structure of zeolite beta.

17. The process of claim 16 in which the organic reactants comprise one or more members selected from the group consisting of acetaldehyde, propionaldehyde, acetone, methylethylketone, butyraldehyde, and crotonaldehyde.

18. The process of claim 17 in which the organic reactants comprise acetaldehyde and formaldehyde, and comprising the additional step of recovering pyridine and beta-picoline as the products of said reacting.

19. The process of claim 17 in which the reactants also include methanol.

20. The process of claim 18 in which the reactants also include methanol.

21. The process of claim 17 in which the reactant is acetaldehyde, and additionally comprising recovering alpha- and gamma-picoline as the products of said reacting.

22. The process of claim 16 in which the zeolite is in acidic form.

23. The process of claim 16 in which the zeolite has been treated with a metal ion or compound.

24. The process of claim 16, wherein the zeolite is formulated with a binder containing silica, alumina, or a combination thereof.

25. The process of claim 16 in which the reactants are a mixture of acetaldehyde, formaldehyde and propionaldehyde, and additionally comprising recovering pyridine and beta-picoline as the products of said reacting.

Referenced Cited
U.S. Patent Documents
3020280 February 1962 Cislak et al.
3020281 February 1962 Cislak et al.
3020282 February 1962 Cislak et al.
3308069 March 1967 Wadlinger et al.
4016218 April 5, 1977 Haag et al.
4220783 September 2, 1980 Chang et al.
4388461 June 14, 1983 Chang et al.
4518485 May 21, 1985 LePierre et al.
4628097 December 9, 1986 Le Blanc et al.
4675410 June 23, 1987 Feitler et al.
4714537 December 22, 1987 Jorgensen et al.
4810794 March 7, 1989 Shimizu et al.
4861894 August 29, 1989 Bowes et al.
4866179 September 12, 1989 Cheng et al.
4910006 March 20, 1990 Zones et al.
5013843 May 7, 1991 Feitler et al.
5164169 November 17, 1992 Rubin
5218122 June 8, 1993 Goe et al.
5304698 April 19, 1994 Husain
5395940 March 7, 1995 Angevine et al.
Foreign Patent Documents
0289924A2 November 1988 EPX
0382543A2 August 1990 EPX
3634259A1 April 1988 DEX
8202884 February 1984 NLX
1235390 June 1971 GBX
WO90/03366 April 1990 WOX
Other references
  • Frillette, V.J., Haag, W.O., Lago, R.M., Catalysis By Crystalline Aluminosilicates: Characterization of Intermediate Pore-Size Zeolites by the "Constraint Index", J. of Catalysis, vol. 67, pp. 218-222 (1981). Haggin, J., "New Zeolite Structures Promising For Catalysis", C & En, p. 8, Dec. 6, 1993. Higgins, J.B., LaPierre, R.B., Schlenker, J.L., Rohrman, A.C., Wood, J.D., Kerr, G.T. Rohrbaugh, W.J., "The Framework Topology Of Zeolite Beta", Zeolites, vol. 8, pp. 446-452, Nov. 1988. Lobo, R.F., Pan, M., Chan, I., Li, H-X., Medrud, R.C., Zones, S.I., Crozier, P.A., Davis, M.E., "SSZ-26 And SSZ-33: Two Molecular Sieves With Intersecting 10-And 12-Ring Pores", Science, vol. 262, pp. 1543-1546, Dec. 3, 1993. Weitkamp, J., Ernst, S., Kumar, R., "The Spaciousness Index: A Novel Test Reaction For Characterizing The Effective Pore Width Of Bifunctional Zeolite Catalysts", Applied Catalysis, vol. 27, pp. 207-210 (1986). Weitkamp, J., Chen, C.Y., Ernst, S., "Characterization Of Zeolites By The Spaciousness Index", Successful Design of Catalysts, pp. 343-350 (1988).
Patent History
Patent number: 5780635
Type: Grant
Filed: Jun 21, 1996
Date of Patent: Jul 14, 1998
Assignee: Reilly Industries, Inc. (Indianapolis, IN)
Inventors: Colin Hugh McAteer (Indianapolis, IN), Douglas Clifford Brown (Indianapolis, IN), Robert Drummond Davis, Sr. (Greencastle, IN)
Primary Examiner: Alan L. Rotman
Law Firm: Woodard, Emhardt, Naughton, Moriarty & McNett
Application Number: 8/668,580
Classifications
Current U.S. Class: The Pyridine Ring Is Unsubstituted Or Hydrocarbyl Substituted Only (546/251); Process Of Forming Pyridine Ring (546/250)
International Classification: C07D21309; C07D21310;